[Technical Field]
[0001] The present disclosure relates to a resin composition for molding and an electronic
component apparatus.
[Background Art]
[0002] In recent years, with the demand for highly functional, light, thin, short, and small
electronic devices, high-density integration and high-density mounting of electronic
components have progressed, and semiconductor packages used in these electronic devices
are becoming smaller and smaller than ever before. Furthermore, the frequency of radio
waves used for communication of electronic devices is also increasing.
[0003] From the viewpoints of dealing with the high frequency and the miniaturization of
semiconductor packages, high dielectric constant epoxy resin compositions used for
sealing semiconductor elements (for example, refer to Patent Literature 1 to 3) have
been proposed.
[Citation List]
[Patent Literature]
[Summary of Invention]
[Technical Problem]
[0005] In recent years, along with the high functionality and the miniaturization of semiconductor
packages (PKGs), development of antenna-in-packages (AiPs) which have an antenna function
is in progress. Examples of materials for sealing an antenna include a resin composition
for molding containing a curable resin, a curing agent, and an inorganic filler. By
using a composition from which a cured product having a high dielectric constant can
be obtained, it is possible to reduce the size ofAiPs.
[0006] On the other hand, in general, a material having a high dielectric constant often
has a high dielectric loss tangent. If a material having a high dielectric loss tangent
is used, transmission signals are converted into heat due to transmission loss, and
communication efficiency is likely to decrease. Here, the amount of transmission loss
generated through heat conversion of radio waves transmitted from communication in
a dielectric is expressed as the product of the frequency, the square root of a relative
dielectric constant, and the dielectric loss tangent. That is, the transmission signal
is likely to be converted into heat proportionally to the frequency. In particular,
in AiPs, the frequency of radio waves used for communication is increased in order
to cope with an increase in the number of channels due to diversification of information.
For this reason, in the resin composition for molding, it is required for both a high
dielectric constant and a low dielectric loss tangent to be achieved in a cured product
after molding.
[0007] In addition, a material having a high dielectric constant sometimes reduces fluidity
of a resin composition for molding. If the fluidity of a resin composition for molding
is low, the moldability may deteriorate and poor appearance such as a flow pattern
(hereinafter, also referred to as a "flow mark") may be caused on the surface of a
cured product after molding. For this reason, favorable moldability is required in
the resin composition for molding.
[0008] An objective of the present disclosure is to provide a resin composition for molding
which has favorable moldability and in which both a high dielectric constant and a
low dielectric loss tangent are achieved in a cured product after molding, and an
electronic component apparatus using the same.
[Solution to Problem]
[0009] Specific means for solving the objective includes the following aspects.
<1> A resin composition for molding including: an epoxy resin; a curing agent; and
an inorganic filler containing at least one selected from the group consisting of
calcium titanate particles and strontium titanate particles, in which a total content
of the calcium titanate particles and the strontium titanate particles is 30% by volume
or more and less than 60% by volume with respect to the entire inorganic filler.
<2> The resin composition for molding according to <1>, in which the curing agent
includes an active ester compound.
<3> The resin composition for molding according to <1> or <2>, in which the inorganic
filler further contains at least one selected from the group consisting of silica
particles and alumina particles.
<4> The resin composition for molding according to <3>, in which the inorganic filler
contains alumina particles.
<5> The resin composition for molding according to any one of <1> to <4>, in which
a relative dielectric constant of the entire inorganic filler at 10 GHz is 80 or less.
<6> The resin composition for molding according to any one of <1> to <5>, in which
a total content of the inorganic filler is 40% by volume to 85% by volume with respect
to the entire resin composition for molding.
<7> The resin composition for molding according to any one of <1> to <6>, which is
used in a high frequency device.
<8> The resin composition for molding according to any one of <1> to <7>, which is
used in an antenna-in-package.
<9> An electronic component apparatus comprising: a support member; an electronic
component placed on the support member; and a cured product of the resin composition
for molding according to any one of <1> to <8> which seals the electronic component.
<10> The electronic component apparatus according to <9>, in which the electronic
component includes an antenna.
[Advantageous Effects of Invention]
[0010] According to the present disclosure, there is provided a resin composition for molding
which has favorable moldability and in which both a high dielectric constant and a
low dielectric loss tangent are achieved in a cured product after molding, and an
electronic component apparatus using the same.
[Description of Embodiments]
[0011] In the present disclosure, the term "step" also includes, in addition to a step independent
of other steps, a step that cannot be clearly distinguished from other steps as long
as the purpose of the step is achieved.
[0012] In the present disclosure, a numerical range indicated using "to" includes numerical
values denoted before and after "to" as a minimum value and a maximum value.
[0013] In a numerical range denoted stepwise in the present disclosure, an upper limit value
or a lower limit value denoted in one numerical range may be substituted with an upper
limit value or a lower limit value of another stepwise numerical range denoted. In
addition, in a numerical range denoted in the present disclosure, an upper limit value
or a lower limit value of the numerical range may be substituted with values shown
in examples.
[0014] Each component in the present disclosure may contain plural kinds of corresponding
substances. In a case where plural kinds of substances corresponding to each component
are present in a composition, the content of each component means a total content
of the plural kinds of corresponding substances present in the composition unless
otherwise specified.
[0015] In the present disclosure, there may be plural kinds of particles corresponding to
components. In a case where plural kinds of particles corresponding to components
are present in a composition, the particle diameter of each component means a value
regarding a mixture of the plural kinds of corresponding particles present in the
composition unless otherwise specified.
[0016] Hereinafter, aspects for implementing the present disclosure will be described in
detail. However, the present disclosure is not limited to the following embodiments.
Constituent elements (including an element step or the like) in the following embodiments
are not essential unless otherwise specified. The same applies to numerical values
and ranges thereof which do not limit the present disclosure.
<Resin Composition for Molding>
[0017] A resin composition for molding according to one embodiment of the present disclosure
includes: an epoxy resin; a curing agent; and an inorganic filler containing at least
one (hereinafter, also referred to as a specific filler) selected from the group consisting
of calcium titanate particles and strontium titanate particles, in which a total content
of the calcium titanate particles and the strontium titanate particles is 30% by volume
or more and less than 60% by volume with respect to the entire inorganic filler.
[0018] As described above, in the resin composition for molding, it is required for both
a high dielectric constant and a low dielectric loss tangent to be achieved in a cured
product after molding. For example, barium titanate can be considered as a material
from which a high dielectric constant can be obtained. However, when barium titanate
is used, not only the dielectric constant but also a dielectric loss tangent is likely
to increase. On the other hand, if the above-described specific filler is used, it
was found that it is possible to increase the dielectric constant and suppress increase
in the dielectric loss tangent compared to the case where barium titanate is used.
That is, in the present embodiment, it is thought that both a high dielectric constant
and a low dielectric loss tangent can be achieved in a cured product after molding
if a specific filler is contained.
[0019] In addition, moldability is required in the resin composition for molding as described
above. However, if the resin composition for molding contains a large amount of specific
fillers, in some cases, fluidity of the resin composition for molding is less likely
to be obtained because the specific fillers have a non-spherical shape, and accordingly,
favorable moldability of the resin composition for molding is less likely to be obtained.
[0020] On the other hand, in the present embodiment, the total content of specific fillers
is 30% by volume or more and less than 60% by volume with respect to the entire inorganic
filler. For this reason, it is thought that fluidity of the resin composition for
molding is obtained and the moldability becomes favorable compared to the case where
the total content of specific fillers is higher than the above-described range.
[0021] For the above-described reasons, it is assumed that the resin composition for molding
of the present embodiment has favorably moldability and both a high dielectric constant
and a low dielectric loss tangent can be achieved in a cured product after molding.
[0022] Hereinafter, each component constituting the resin composition for molding will be
described. The resin composition for molding of the present embodiment may contain
an epoxy resin, a curing agent, and an inorganic filler, and may contain other components
as necessary.
(Epoxy Resin)
[0023] The type of epoxy resin is not particularly limited as long as an epoxy resin has
an epoxy group in a molecule.
[0024] Specific examples of epoxy resins include: novolac-type epoxy resins (such as a phenol
novolac-type epoxy resin and an ortho-cresol novolac epoxy resin) which are obtained
by epoxidizing novolac resins and condensing or co-condensing at least one phenolic
compound selected from the group consisting of a phenol compound such as phenol, cresol,
xylenol, resorcin, catechol, bisphenol A, or bisphenol F and a naphthol compound such
as α-naphthol, β-naphthol, or dihydroxynaphthalene, and an aliphatic aldehyde compound
such as formaldehyde, acetaldehyde, or propionaldehyde in the presence of an acidic
catalyst; triphenylmethane-type epoxy resins which are obtained by epoxidizing triphenylmethane-type
phenol resins and condensing or co-condensing the above-described phenolic compounds
and an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde in the presence
of an acidic catalyst; copolymerization-type epoxy resins which are obtained by epoxidizing
novolac resins and co-condensing the above-described phenol compounds and naphthol
compounds, and an aldehyde compound in the presence of an acidic catalyst; diphenylmethane-type
epoxy resins which are diglycidyl ethers of bisphenol A and bisphenol F; biphenyl-type
epoxy resins which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenyl;
stilbene-type epoxy resins such as diglycidyl ethers of stilbene-based phenol compounds;
sulfur atom-containing epoxy resins which are diglycidyl ethers of bisphenol S; epoxy
resins which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol,
and polypropylene glycol; glycidyl ester-type epoxy resins which are glycidyl esters
of polyhydric carboxylic acid compounds such as phthalic acid, isophthalic acid, and
tetrahydrophthalic acid; glycidyl amine-type epoxy resins obtained by substituting
active hydrogen bound to a nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric
acid, or the like with a glycidyl group; dicyclopentadiene-type epoxy resins obtained
by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound;
alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,
and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane which are obtained
by epoxidizing an olefin bond in a molecule; para-xylene-modified epoxy resins which
are glycidyl ethers of para-xylene-modified phenol resins; meta-xylene-modified epoxy
resins which are glycidyl ethers of meta-xylene-modified phenol resins; terpene-modified
epoxy resins which are glycidyl ethers of terpene-modified phenol resins; dicyclopentadiene-modified
epoxy resins which are glycidyl ethers of dicyclopentadiene-modified phenol resins;
cyclopentadiene-modified epoxy resins which are glycidyl ethers of cyclopentadiene-modified
phenol resins; polycyclic aromatic ring-modified epoxy resins which are glycidyl ethers
of polycyclic aromatic ring-modified phenol resins; naphthalene-type epoxy resins
which are glycidyl ethers of naphthalene-containing phenol resins; halogenated phenol
novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type
epoxy resins; linear aliphatic epoxy resins obtained by oxidizing an olefin bond with
a peracid such as peracetic acid; and aralkyl-type epoxy resins obtained by epoxidizing
aralkyl-type phenol resins such as a phenol aralkyl resin and a naphthol aralkyl resin.
Furthermore, an epoxidized material or the like of an acrylic resin may also be exemplified
as an epoxy resin. These epoxy resins may be used alone or in a combination of two
or more thereof.
[0025] The epoxy equivalent (molecular weight/number of epoxy groups) of an epoxy resin
is not particularly limited. From the viewpoints of balancing various characteristics
such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent
of an epoxy resin is preferably 100 g/eq to 1,000 g/eq and more preferably 150 g/eq
to 500 g/eq.
[0026] A value measured through a method according to JIS K 7236:2009 is used as an epoxy
equivalent of an epoxy resin.
[0027] In a case where an epoxy resin is a solid, the softening point or the melting point
of an epoxy resin is not particularly limited. The softening point or the melting
point of an epoxy resin is preferably 40°C to 180°C from the viewpoints of moldability
and reflow resistance and more preferably 50°C to 130°C from the viewpoint of handleability
when preparing a resin composition for molding.
[0028] A value measured through differential scanning calorimetry (DSC) or a method (ring
and ball method) according to JIS K 7234:1986 is used as a melting point or a softening
point of an epoxy resin.
[0029] The mass proportion of an epoxy resin in the total amount of a resin composition
for molding is, from the viewpoints of strength, fluidity, heat resistance, moldability,
and the like, preferably 0.5 mass% to 30 mass%, more preferably 2 mass% to 20 mass%,
and still more preferably 3.5 mass% to 13 mass%.
(Curing Agent)
[0030] The resin composition for molding in the present embodiment contains a curing agent.
The type of curing agent is not particularly limited.
[0031] A curing agent preferably includes an active ester compound. The active ester compound
may be used alone or in a combination of two or more thereof. Here, the active ester
compound refers to a compound which has one or more ester groups reacting with an
epoxy group in one molecule and has an action of curing an epoxy resin. In a case
where a curing agent includes an active ester compound, the curing agent may or may
not include a curing agent in addition to the active ester compound.
[0032] If an active ester compound is used as a curing agent, the dielectric loss tangent
of a cured product can be reduced to a low level compared to a case where a phenol
curing agent or an amine curing agent is used as a curing agent. The reason is assumed
as follows.
[0033] In a reaction between an epoxy resin and a phenol curing agent or an amine curing
agent, a secondary hydroxyl group is produced. On the other hand, in a reaction between
an epoxy resin and an active ester compound, an ester group is produced instead of
a secondary hydroxyl group. Since an ester group has a lower polarity than a secondary
hydroxyl group, a resin composition for molding containing an active ester compound
as a curing agent can reduce the dielectric loss tangent of a cured product to a low
level compared to a resin composition for molding containing only a curing agent that
produces a secondary hydroxyl group as a curing agent.
[0034] In addition, since a polar group in a cured product enhances water absorbability
of the cured product, the concentration of the polar group in the cured product can
be reduced and the water absorbability of the cured product can be suppressed using
an active ester compound as a curing agent. By suppressing the water absorbability
of a cured product, that is, by suppressing the content of H
2O which is a polar molecule, the dielectric loss tangent of the cured product can
be further reduced to a low level.
[0035] The type of active ester compound is not particularly limited as long as it is a
compound having one or more ester groups reacting with an epoxy group in a molecule.
Examples of active ester compounds include a phenol ester compound, a thiophenol ester
compound, an N-hydroxyamine ester compound, and an esterified substance of a heterocyclic
hydroxy compound.
[0036] Examples of active ester compounds include an ester compound obtained from at least
one kind of an aliphatic carboxylic acid or an aromatic carboxylic acid and at least
one kind of an aliphatic hydroxy compound or an aromatic hydroxy compound. Ester compounds
which have aliphatic compounds as components of polycondensation and have aliphatic
chains tend to have excellent compatibility with epoxy resins. Ester compounds which
have aromatic compounds as components of polycondensation and have aromatic rings
tend to have excellent heat resistance.
[0037] Specific examples of active ester compounds include aromatic esters obtained by a
condensation reaction between aromatic carboxylic acids and phenolic hydroxyl groups.
Among these, aromatic esters obtained by a condensation reaction between aromatic
carboxylic acids and phenolic hydroxyl groups using a mixture of an aromatic carboxylic
acid component in which 2 to 4 hydrogen atoms of aromatic rings such as benzene, naphthalene,
biphenyl, diphenylpropane, diphenylmethane, diphenyl ethers, and diphenyl sulfonic
acid are substituted with carboxy groups, a monovalent phenol in which one hydrogen
atom of the aromatic ring is substituted with a hydroxyl group, and a polyhydric phenol
in which 2 to 4 hydrogen atoms of the aromatic rings are substituted with hydroxyl
groups as a raw material are preferable. That is, aromatic esters having a structural
unit derived from the above-described aromatic carboxylic acid component, a structural
unit derived from the above-described monovalent phenol, and a structural unit derived
from the above-described polyhydric phenol are preferable.
[0038] Specific examples of active ester compounds include an active ester resin which is
disclosed in
Japanese Patent Laid-Open No. 2012-246367 and has a structure obtained by reacting a phenol resin having a molecular structure
in which a phenol compound is knotted via an alicyclic hydrocarbon group, an aromatic
dicarboxylic acid or a halide thereof, and an aromatic monohydroxy compound. Compounds
represented by Structural Formula (1) below are preferable as the active ester resins.

[0039] In Structural Formula (1), R
1 is an alkyl group having 1 to 4 carbon atoms, X is an unsubstituted benzene ring,
an unsubstituted naphthalene ring, a benzene ring or a naphthalene ring substituted
with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, Y is a benzene
ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with
an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n is 0.25 to 1.5 representing
an average repeating number.
[0041] Specific examples of other active ester compounds include compounds represented by
Structural Formula (2) below and compounds represented by Structural Formula (3) below
which are disclosed in
Japanese Patent Laid-Open No. 2014-114352.

[0042] In Structural Formula (2), R
1 and R
2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon
atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is an ester-forming structure
moiety (z1) selected from the group consisting of an unsubstituted benzoyl group,
an unsubstituted naphthoyl group, a benzoyl group or a naphthoyl group substituted
with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon
atoms, or a hydrogen atom (z2), in which at least one Z is the ester-forming structure
moiety (z1).
[0043] In Structural Formula (3), R
1 and R
2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon
atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is an ester-forming structure
moiety (z1) selected from the group consisting of an unsubstituted benzoyl group,
an unsubstituted naphthoyl group, a benzoyl group or a naphthoyl group substituted
with an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 6 carbon
atoms, or a hydrogen atom (z2), in which at least one Z is the ester-forming structure
moiety (z1).
[0044] Specific examples of the compounds represented by Structural Formula (2) include
exemplary compounds (2-1) to (2-6) below.

[0045] Specific examples of the compounds represented by Structural Formula (3) include
exemplary compounds (3-1) to (3-6) below.

[0046] Commercially available products may be used as active ester compounds. Examples of
commercially available products of active ester compounds include "EXB9451," "EXB9460,"
"EXB9460S," and "HPC-8000-65T" (manufactured by DIC CORPORATION) as active ester compounds
having a dicyclopentadiene-type diphenol structure; "EXB9416-70BK," "EXB-8," and "EXB-9425"
(manufactured by DIC CORPORATION) as active ester compounds having an aromatic structure;
"DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound
containing a phenol novolac acetylated product; and "YLH1026" (manufactured by Mitsubishi
Chemical Corporation) as an active ester compound containing a benzoylated product
of phenol novolac.
[0047] The ester equivalent (molecular weight/number of ester groups) of an active ester
compound is not particularly limited. From the viewpoints of balancing various characteristics
such as moldability, reflow resistance, and electrical reliability, the ester equivalent
thereof is preferably 150 g/eq to 400 g/eq, more preferably 170 g/eq to 300 g/eq,
and still more preferably 200 g/eq to 250 g/eq.
[0048] A value measured through a method according to JIS K 0070:1992 is used as an ester
equivalent of an active ester compound.
[0049] The equivalent ratio (ester group/epoxy group) of an active ester compound to an
epoxy resin is, from the viewpoint of reducing the dielectric loss tangent of a cured
product to a low level, preferably 0.9 or more, more preferably 0.95 or more, and
still more preferably 0.97 or more.
[0050] The equivalent ratio (ester group/epoxy group) of an active ester compound to an
epoxy resin is, from the viewpoint of reducing the content of active ester compound
unreacted, preferably 1.1 or less, more preferably 1.05 or less, and still more preferably
1.03 or less.
[0051] A curing agent may include other curing agents in addition to the active ester compound.
The types of other curing agents are not particularly limited and can be selected
according to desired properties of a resin composition for molding. Examples of other
curing agents include a phenol curing agent, an amine curing agent, an acid anhydride
curing agent, a polymercaptan curing agent, a polyaminoamide curing agent, isocyanate
curing agent, and a blocked isocyanate curing agent.
[0052] Specific examples of phenol curing agents include polyhydric phenol compounds such
as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted
biphenol; novolac-type phenol resins obtained by condensing or co-condensing at least
one phenolic compound selected from the group consisting of a phenol compound such
as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol,
or aminophenol and a naphthol compound such as α-naphthol, β-naphthol, or dihydroxynaphthalene,
and an aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde in
the presence of an acidic catalyst; aralkyl-type phenol resins such as naphthol aralkyl
resins and phenol aralkyl resins synthesized from dimethoxy para-xylene, bis(methoxymethyl)biphenyl,
and the like and the above-described phenolic compounds; para-xylene-modified phenol
resins and meta-xylene-modified phenol resins; melamine-modified phenol resins; terpene-modified
phenol resins; dicyclopentadiene-type naphthol resins and dicyclopentadiene-type phenol
resins synthesized through copolymerization of dicyclopentadiene and the above-described
phenolic compounds; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified
phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins and
condensing or co-condensing the above-described phenolic compounds and an aromatic
aldehyde compound such as benzaldehyde or salicylaldehyde in the presence of an acidic
catalyst; and phenol resins obtained through copolymerization of two or more of these.
These phenol curing agents may be used alone or in a combination of two or more thereof.
[0053] The functional group equivalents (the hydroxyl equivalent in a case of a phenol curing
agent) of other curing agents are not particularly limited. From the viewpoints of
balancing various characteristics such as moldability, reflow resistance, and electrical
reliability, the functional group equivalents of other curing agents are preferably
70 g/eq to 1,000 g/eq and more preferably 80 g/eq to 500 g/eq.
[0054] Values measured through a method according to JIS K0070:1992 are used as functional
group equivalents (a hydroxyl equivalent in a case of a phenol curing agent) of other
curing agents.
[0055] The softening point or the melting point of a curing agent is not particularly limited.
The softening point or the melting point of a curing agent is preferably 40°C to 180°C
from the viewpoints of moldability and reflow resistance and more preferably 50°C
to 130°C from the viewpoint of handleability when producing a resin composition for
molding.
[0056] A value measured in the same manner as the melting point or the softening point of
an epoxy resin is used as a melting point or a softening point of a curing agent.
[0057] The equivalent ratio of an epoxy resin to a curing agent (all curing agents in a
case where plural kinds of curing agents are used), that is, the ratio (number of
functional groups in curing agent/number of functional groups in epoxy resin) of the
number of functional groups in a curing agent to the number of functional groups in
an epoxy resin, is not particularly limited. From the viewpoint of reducing unreacted
contents, the ratio is preferably set in a range of 0.5 to 2.0 and more preferably
set in a range of 0.6 to 1.3. From the viewpoints of moldability and reflow resistance,
the ratio is more preferably set in a range of 0.8 to 1.2.
[0058] In a case where a curing agent includes an active ester compound and other curing
agents, the mass proportion of the active ester compound in the total amount of the
active ester compound and the other curing agents is, from the viewpoint of reducing
the dielectric loss tangent of a cured product to a low level, preferably 80 mass%
or more, more preferably 85 mass% or more, and still more preferably 90 mass% or more.
[0059] In a case where a curing agent includes an active ester compound and other curing
agents, the total mass proportion of the active ester compound and an epoxy resin
in the total amount of curing agents and the epoxy resin is, from the viewpoint of
reducing the dielectric loss tangent of a cured product to a low level, preferably
80 mass% or more, more preferably 85 mass% or more, and still more preferably 90 mass%
or more.
(Curing Promoter)
[0060] The resin composition for molding in the present embodiment may contain a curing
promoter as necessary. The type of curing promoter is not particularly limited and
can be selected according to, for example, the type of epoxy resin or curing agent
and desired properties of a resin composition for molding.
[0061] Examples of curing promoters include cyclic amidine compounds such as a diazabicycloalkene
including 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1,8-diazabicyclo[5.4.0]undecene-7
(DBU), 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole,
and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac
salts of the cyclic amidine compounds or derivatives thereof; compounds with intramolecular
polarization obtained by adding a compound having a π bond, such as maleic anhydride,
a quinone compound including 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone,
2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone,
2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, or diazophenylmethane
to those compounds; cyclic amidinium compounds such as a tetraphenylborate salt of
DBU, a tetraphenylborate salt of DBN, a tetraphenylborate salt of 2-ethyl-4-methylimidazole,
and a tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such
as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine,
dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the tertiary
amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium
phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium
hydroxide; organic phosphines such as primary phosphines including ethylphosphine
and phenylphosphine, secondary phosphines such as dimethylphosphine and diphenylphosphine,
and tertiary phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine,
tris(alkoxyphenyl)phosphine, tris(alkyl-alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine,
tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine,
tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine,
dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, and tris(benzyl)phosphine;
phosphine compounds such as a complex of the organic phosphines and organic borons;
compounds with intramolecular polarization obtained by adding a compound having a
π bond, such as maleic anhydride, a quinone compound including 1,4-benzoquinone, 2,5-toluquinone,
1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone,
2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, or diazophenylmethane
to the organic phosphines or the phosphine compounds; compounds with intramolecular
polarization obtained by reacting the organic phosphines or the phosphine compounds
with halogenated phenolic compounds such as 4-bromophenol, 3-bromophenol, 2-bromophenol,
4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol,
4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol,
4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol,
and 4-bromo-4'-hydroxybiphenyl, and then performing a process of dehydrohalogenation;
tetra-substituted phosphonium compounds such as tetra-substituted phosphonium including
tetraphenylphosphonium, a tetraphenylborate salt of tetra-substituted phosphonium
including tetraphenylphosphonium tetra-p-tolylborate, and salts of tetra-substituted
phosphonium with a phenol compound; salts of tetraalkylphosphonium with partial hydrolysates
of aromatic carboxylic acid anhydride; phosphobetaine compounds; and adducts of phosphonium
compounds and silane compounds.
[0062] The curing promoters may be used alone or in a combination of two or more thereof.
[0063] Among these, examples of particularly suitable curing promoters include triphenylphosphine,
adducts of triphenylphosphine and quinone compounds, adducts of tributylphosphine
and quinone compounds, and adducts of tri-p-tolylphosphine.
[0064] In a case where the resin composition for molding contains a curing promoter, the
amount of curing promoter is, based on 100 parts by mass of resin components (a total
amount of an epoxy resin and a curing agent), preferably 0.1 parts by mass to 30 parts
by mass and more preferably 1 part by mass to 15 parts by mass. If the amount of curing
promoter is 0.1 parts by mass or more with respect to 100 parts by mass of resin components,
curing tends to favorably occur in a short period of time. If the amount of curing
promoter is 30 parts by mass or less with respect to 100 parts by mass of resin components,
the curing rate is not too fast and favorable molded products tend to be obtained.
(Inorganic Filler)
[0065] The resin composition for molding in the present embodiment contains an inorganic
filler containing a specific filler (that is, at least one selected from the group
consisting of calcium titanate particles and strontium titanate particles). Moreover,
the total content of specific fillers is 30% by volume or more and less than 60% by
volume with respect to an entire inorganic filler. That is, an inorganic filler includes
a specific filler and other fillers in addition to the specific filler.
-Specific Filler-
[0066] A specific filler may contain any one of calcium titanate particles or strontium
titanate particles and may contain both calcium titanate particles and strontium titanate
particles.
[0067] Among these, a specific filler preferably contains calcium titanate particles.
[0068] Calcium titanate particles and strontium titanate particles may be surface-treated.
[0069] The total content of specific fillers is 30% by volume or more and less than 60%
by volume with respect to an entire inorganic filler. From the viewpoint of obtaining
a cured product with a high dielectric constant, the total content of specific fillers
is, based on an entire inorganic filler, preferably 35% by volume or more and more
preferably 40% by volume or more. From the viewpoint of moldability, the total content
of specific fillers is, based on an entire inorganic filler, preferably 55% by volume
or less and more preferably 50% by volume or less. Moreover, from the viewpoint of
achieving both favorable moldability and high dielectric constant, the total content
of specific fillers is, based on an entire inorganic filler, preferably 35% by volume
to 55% by volume and more preferably 40% by volume to 50% by volume.
[0070] The content (% by volume) of specific fillers in an entire inorganic filler can be
obtained through the following method.
[0071] A thin sample of a cured product of a resin composition for molding is imaged with
a scanning electron microscope (SEM). An arbitrary area S is specified in the SEM
image, and a total area A of an inorganic filler contained in the area S is obtained.
Next, elements of the inorganic filler are specified using an energy dispersive X-ray
spectroscope (SEM-EDX) to obtain a total area B of specific fillers contained in the
total area A of the inorganic filler. A value obtained by dividing the total area
B of the specific fillers by the total area A of the inorganic filler is converted
into a percentage (%), and this value is taken as a content (% by volume) of calcium
titanate particles in the entire inorganic filler.
[0072] The area S is a sufficiently large area with respect to the size of the inorganic
filler. For example, the area S is sized to contain 100 or more inorganic fillers.
The area S may be the sum of a plurality of cut surfaces.
[0073] The total content of specific fillers is 15% by volume or more and less than 40%
by volume with respect to an entire resin composition for molding. From the viewpoint
of obtaining a cured product with a high dielectric constant, the total content of
specific fillers is, based on an entire resin composition for molding, more preferably
25% by volume or more and still more preferably 27% by volume or more. From the viewpoint
of moldability, the total content of specific fillers is, based on an entire resin
composition for molding, more preferably 35% by volume or less and still more preferably
33% by volume or less. Moreover, from the viewpoint of achieving both favorable moldability
and high dielectric constant, the total content of specific fillers is, based on an
entire resin composition for molding, more preferably 25% by volume to 35% by volume
and still more preferably 27% by volume to 33% by volume.
[0074] The volume average particle diameter of specific fillers is preferably 0.1 m to 100
µm and more preferably 0.5 µm to 30 µm.
[0075] The volume average particle diameter of specific fillers can be measured as follows.
A resin composition for molding is placed in a melting pot and allowed to stand at
800°C for 4 hours to be incinerated. The obtained ash can observed with SEM and separated
according to the shape, a particle size distribution can be obtained from the observation
image, and a volume average particle diameter of specific fillers can be obtained
as a volume average particle diameter (D50) from the particle size distribution.
[0076] Specific fillers may be a mixture of two or more kinds of fillers having different
volume average particle diameters.
[0077] The shapes of specific fillers are not particularly limited, and examples thereof
include a spherical shape, an elliptical shape, and an amorphous shape. In addition,
specific fillers may be crushed.
-Other Fillers-
[0078] The types of other fillers are not particularly limited. Specific examples of materials
for other fillers include inorganic materials such as fused silica, crystal silica,
glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride,
aluminum nitride, boron nitride, beryllia, zirconia, zircon, forsterite, steatite,
spinel, mullite, titania, talc, clay, and mica.
[0079] Inorganic fillers having a flame-retardant effect may be used as the other fillers.
Examples of inorganic fillers having a flame-retardant effect include aluminum hydroxide,
magnesium hydroxide, a composite metal hydroxide such as a composite hydroxide of
zinc and magnesium, and zinc borate.
[0080] The other fillers may be used alone or in a combination of two or more thereof.
[0081] Among these, the other fillers preferably contain at least one selected from the
group consisting of silica particles and alumina particles from the viewpoints that
the filling rate can be improved with a spherical shape, the dielectric constant is
lower than that of a specific inorganic filler, and the dielectric properties of a
composite material can be controlled. The other fillers may contain only one of silica
particles and alumina particles and contain both silica particles and alumina particles.
[0082] In a case where the other fillers contain at least one selected from the group consisting
of silica particles and alumina particles, the total content of the silica particles
and the alumina particles is, based on an entire inorganic filler, preferably 40%
by volume to 70% by volume, more preferably 45% by volume to 65% by volume, and still
more preferably 50% by volume to 60% by volume.
[0083] The other fillers preferably contain alumina particles from the viewpoint of increasing
fluidity of a resin composition for molding.
[0084] In a case where the other fillers contain alumina particles, the content of the alumina
particles is, based on an entire inorganic filler, preferably 40% by volume to 70%
by volume, more preferably 45% by volume to 65% by volume, and still more preferably
50% by volume to 60% by volume.
[0085] From the viewpoint of reducing the dielectric loss tangent of a cured product to
a low level, the content of barium titanate based on an entire inorganic filler is
preferably less than 10% by volume, more preferably less than 5% by volume, and still
more preferably less than 1% by volume.
[0086] The volume average particle diameter of other fillers is not particularly limited.
The volume average particle diameter of other fillers is preferably 0.2 µm to 100
µm and more preferably 0.5 µm to 50 µm. When the volume average particle diameter
of other fillers is 0.2 µm or more, the increase in the viscosity of a resin composition
for molding tends to be further suppressed. When the volume average particle diameter
of other fillers is 100 µm or less, the filling properties of a resin composition
for molding tend to be further improved.
[0087] The average particle diameter of other inorganic fillers can be measured as follows.
A resin composition for molding is placed in a melting pot and allowed to stand at
800°C for 4 hours to be incinerated. The obtained ash can observed with SEM and separated
according to the shape, a particle size distribution can be obtained from the observation
image, and a volume average particle diameter of other fillers can be obtained as
a volume average particle diameter (D50) from the particle size distribution.
[0088] Other fillers may be a mixture of two or more kinds of fillers having different volume
average particle diameters.
[0089] The shapes of other fillers are not particularly limited, and examples thereof include
a spherical shape, an elliptical shape, and an amorphous shape. In addition, other
fillers may be crushed.
[0090] Other fillers preferably have a spherical shape from the viewpoint of improving fluidity
of a resin composition for molding.
-Total Content and Characteristics of Inorganic fillers-
[0091] The total content of inorganic fillers contained in a resin composition for molding
is, from the viewpoint of controlling strength and fluidity of a cured product of
the resin composition for molding, preferably 40% by volume to 90% by volume of the
entire resin composition for molding, more preferably 40% by volume to 85% by volume
thereof, still more preferably 45% by volume to 85% by volume thereof, particularly
preferably 50% by volume to 82% by volume thereof, and significantly preferably 55%
by volume to 80% by volume.
[0092] The content (% by volume) of inorganic fillers in a resin composition for molding
can be obtained through the following method.
[0093] A thin sample of a cured product of a resin composition for molding is imaged with
a scanning electron microscope (SEM). An arbitrary area S is specified in the SEM
image, and a total area A of inorganic fillers contained in the area S is obtained.
A value obtained by dividing the total area A of the inorganic fillers by the area
S is converted into a percentage (%), and this value is taken as a content (% by volume)
of the inorganic fillers in the resin composition for molding.
[0094] The area S is a sufficiently large area with respect to the size of the inorganic
fillers. For example, the area S is sized to contain 100 or more inorganic fillers.
The area S may be the sum of a plurality of cut surfaces.
[0095] The inorganic fillers may cause a bias in the abundance ratio in the gravity direction
during curing of the resin composition for molding. In that case, when an image is
taken with SEM, the entire gravity direction of the cured product is imaged, and the
area S including the entire gravity direction of the cured product is specified.
[0096] The range of the relative dielectric constant (hereinafter, also referred to as a
"dielectric constant") of an entire inorganic filler at 10 GHz is, for example, 80
or less.
[0097] Examples of methods of setting the total content of specific fillers to 30% by volume
or more and less than 60% by volume with respect to the entire inorganic filler and
setting the dielectric constant of the entire inorganic filler to 80 or less include
a method of using non-calcined specific fillers as specific fillers. Here, the non-calcined
specific fillers refer to specific fillers that have not been exposed to a temperature
of 1000°C or higher after being synthesized.
[0098] The dielectric constant of specific fillers is greatly increased through calcining
at a temperature of 1000°C or higher. For example, the dielectric constant after non-calcined
calcium titanate is calcined at a temperature of 1000°C for 2 hours is 10 times or
more of the dielectric constant of calcium titanate before calcination.
[0099] For this reason, in a case where the dielectric constant of the entire inorganic
filler is adjusted to 80 or less while using calcined specific fillers as specific
fillers, the total content of the specific fillers in the entire inorganic filler
is lowered. Moreover, in a resin composition for molding in which an inorganic filler
containing calcined specific fillers at a low content and having a dielectric constant
in the total of the inorganic filler of 80 or less is used, although a cured product
having a high dielectric constant can be obtained, unevenness in the dielectric constant
in the cured product is likely to occur. On the other hand, in a resin composition
for molding in which an inorganic filler containing non-calcined specific fillers
at a content of 30% by volume or more and less than 60% by volume and having a dielectric
constant in the total of the inorganic filler of 80 or less is used, a cured product
having a high dielectric constant and high uniformity in the dielectric constant can
be obtained.
[0100] The dielectric constant of the entire inorganic filler is, from the viewpoint of
suppressing dielectric loss, preferably 50 or less, more preferably 40 or less, and
still more preferably 30 or less. The dielectric constant of the entire inorganic
filler is, from the viewpoint of miniaturization of electronic components such as
an antenna, preferably 5 or more, more preferably 10 or more, and still more preferably
15 or more. The dielectric constant of the entire inorganic filler is, from the viewpoints
of suppression of dielectric loss and miniaturization of electronic components such
as an antenna, preferably 5 to 50, more preferably 10 to 40, and still more preferably
15 to 30.
[0101] Here, the dielectric constant of the entire inorganic filler is obtained, for example,
as follows.
[0102] Specifically, three or more kinds of resin compositions for measurement which contain
inorganic fillers to be measured and a specific curable resin and have different contents
of the inorganic fillers and a resin composition for measurement contains the specific
curable resin but no inorganic filler are prepared. Examples of the resin compositions
for measurement which contain inorganic fillers to be measured and a specific curable
resin include resin compositions for measurement containing a biphenyl aralkyl-type
epoxy resin, a phenol curing agent which is a phenol aralkyl-type phenol resin, a
curing promoter containing organic phosphine, and inorganic fillers to be measured.
In addition, examples of three or more resin compositions for measurement having different
contents of inorganic fillers include resin compositions for measurement having contents
of inorganic fillers of 10% by volume, 20% by volume, and 30% by volume with respect
to the entire resin compositions for measurement.
[0103] Each of the resin compositions for measurement prepared are molded through compression
molding under the conditions of a mold temperature of 175°C, a molding pressure of
6.9 MPa, and a curing time of 600 seconds to obtain respective cured products for
measurement. The relative dielectric constant of each of the cured products for measurement
obtained at 10 GHz is measured, and a graph is created in which the contents of inorganic
fillers are plotted on the lateral axis and the measurement values of the relative
dielectric constants are plotted on the longitudinal axis. From the obtained graph,
linear approximation is performed through a least-squares method, and the relative
dielectric constant when the contents of inorganic fillers are 100% by volume is obtained
through extrapolation and used as "dielectric constants of the entire inorganic filler."
[Various Additives]
[0104] The resin composition for molding in the present embodiment may contain, in addition
to the above-described components, various kinds of additives such as a coupling agent,
an ion exchanger, a releasing agent, a flame retardant, a coloring agent, and a stress
relaxation agent exemplified below. The resin composition for molding in the present
embodiment may contain various kinds of additives well known in the technical field
as necessary in addition to additives exemplified below.
(Coupling Agent)
[0105] The resin composition for molding in the present embodiment may contain a coupling
agent. From the viewpoint of enhancing adhesiveness between resin components and inorganic
fillers, the resin composition for molding preferably contains a coupling agent. Examples
of coupling agents include well-known coupling agents such as silane compounds including
epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane,
and disilazane, titanium compounds, aluminum chelate compounds, and aluminum-zirconium
compounds.
[0106] In a case where the resin composition for molding contains a coupling agent, the
amount of coupling agent is, based on 100 parts by mass of inorganic fillers, preferably
0.05 parts by mass to 5 parts by mass and more preferably 0.1 parts by mass to 2.5
parts by mass. If the amount of coupling agent is 0.05 parts by mass or more with
respect to 100 parts by mass of inorganic fillers, the adhesiveness with a frame tends
to be further improved. If the amount of coupling agent is 5 parts by mass or less
with respect to 100 parts by mass of inorganic fillers, the moldability of a package
tends to be further improved.
(Ion Exchanger)
[0107] The resin composition for molding in the present embodiment may contain an ion exchanger.
The resin composition for molding preferably contains an ion exchanger from the viewpoint
of improving high-temperature shelf properties and moisture resistance of an electronic
component apparatus including electronic components to be sealed. The ion exchanger
is not particularly limited, and well-known ones in the related art can be used. Examples
thereof include hydrotalcite compounds and hydrous oxides of at least one selected
from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth.
The ion exchangers may be used alone or in a combination of two or more thereof. Among
these, hydrotalcite represented by General Formula (A) below is preferable.
Mg
(1-x)AL
x(OH)
2(CO
3)
x/2·mH
2O ...... (A)
(0<X≤0.5, m is a positive number)
[0108] In a case where the resin composition for molding contains an ion exchanger, the
content thereof is not particularly limited as long as it is an amount sufficient
to capture ions such as halogen ions. For example, the content of an ion exchanger
is, based on 100 parts by mass of resin components (a total amount of an epoxy resin
and a curing agent), preferably 0.1 parts by mass to 30 parts by mass and more preferably
1 part by mass to 10 parts by mass.
(Releasing Agent)
[0109] The resin composition for molding in the present embodiment may contain a releasing
agent from the viewpoint of obtaining favorable releasability from a mold during molding.
The releasing agent is not particularly limited, and well-known ones in the related
art can be used. Specific examples thereof include carnauba wax, higher fatty acids
such as montanic acid and stearic acid, higher fatty acid metal salts, ester-based
wax including montanic acid esters, and polyolefin-based wax including polyethylene
oxides and non-oxidized polyethylene. The releasing agents may be used alone or in
a combination of two or more thereof.
[0110] In a case where the resin composition for molding contains a releasing agent, the
amount of releasing agent is, based on 100 parts by mass of resin components (a total
amount of an epoxy resin and a curing agent), preferably 0.01 parts by mass to 10
parts by mass and more preferably 0.1 parts by mass to 5 parts by mass. If the amount
of releasing agent is 0.01 parts by mass or more with respect to 100 parts by mass
of resin components, the sufficient releasability tends to be obtained. If the amount
of releasing agent is 10 parts by mass or less, more favorable adhesiveness tends
to be obtained.
(Flame Retardant)
[0111] The resin composition for molding in the present embodiment may contain a flame retardant.
The flame retardant is not particularly limited, and well-known ones in the related
art can be used. Specific examples thereof include organic or inorganic compounds
containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and
metal hydroxides. The flame retardants may be used alone or in a combination of two
or more thereof.
[0112] In a case where the resin composition for molding contains a flame retardant, the
amount thereof is not particularly limited as long as it is an amount sufficient to
obtain a desired flame-retardant effect. For example, the amount thereof is, based
on 100 parts by mass of resin components (a total amount of an epoxy resin and a curing
agent), preferably 1 part by mass to 30 parts by mass and more preferably 2 parts
by mass to 20 parts by mass.
(Coloring Agent)
[0113] The resin composition for molding in the present embodiment may contain a coloring
agent. Examples of coloring agents include well-known coloring agents such as carbon
black, organic dyes, organic pigments, titanium oxide, red lead, and red oxide. The
content of a coloring agent can be appropriately selected depending on the purpose
and the like. The coloring agents may be used alone or in a combination of two or
more thereof.
(Stress Relaxation Agent)
[0114] The resin composition for molding in the present embodiment may contain a stress
relaxation agent. If the resin composition for molding contains a stress relaxation
agent, warpage deformation of a package and generation of package cracks can be further
reduced. Examples of stress relaxation agents include generally used well-known stress
relaxation agents (flexible agents). Specific examples thereof include thermoplastic
elastomers based on silicone, styrene, olefin, urethane, polyester, polyether, polyamides,
polybutadiene, and the like; rubber particles such as natural rubber (NR), acrylonitrile-butadiene
rubber (NBR), acrylic rubber, urethane rubber, and silicone powder; and rubber particles,
such as a methyl methacrylate-styrene-butadiene copolymer (MBS), a methyl methacrylate-silicone
copolymer, and a methyl methacrylate-butyl acrylate copolymer, having a core-shell
structure. The stress relaxation agents may be used alone or in a combination of two
or more thereof.
[0115] Among the stress relaxation agents, a silicone-based stress relaxation agent is preferable.
Examples of silicone-based stress relaxation agents include one having an epoxy group,
one having an amino group, and one obtained by modifying these with polyether, and
a silicone compound having an epoxy group and a silicone compound such as a polyether-based
silicone compound are more preferable.
[0116] In a case where the resin composition for molding contains a stress relaxation agent,
the amount of stress relaxation agent is, based on 100 parts by mass of resin components
(a total amount of an epoxy resin and a curing agent), for example, preferably 1 part
by mass to 30 parts by mass and more preferably 2 parts by mass to 20 parts by mass.
(Method for Preparing Resin Composition for Molding)
[0117] A method for preparing a resin composition for molding is not particularly limited.
Examples of general methods include a method for sufficiently mixing predetermined
formulation amounts of components with a mixer or the like, followed by melt-kneading
the mixture with a mixing roll, an extruder, and the like, and cooling and pulverizing
the mixture. More specific examples thereof include a method for stirring and mixing
predetermined amounts of the above-described components, kneading the mixture with
an extruder, a roll, a kneader, and the like preheated to 70°C to 140°C, and cooling
and pulverizing the mixture.
[0118] The resin composition for molding in the present embodiment is preferably a solid
at normal temperature and pressure (for example, at 25°C under atmospheric pressure).
The shape of the resin composition for molding in a case where the resin composition
for molding is a solid is not particularly limited, but examples thereof include a
powdery shape, a granular shape, and a tablet shape. The resin composition for molding
in a case where the resin composition for molding is a tablet shape preferably has
dimensions and mass that suit molding conditions of a package from the viewpoint of
handleability.
(Characteristics of Resin Composition for Molding)
[0119] The relative dielectric constant of a cured product, obtained by molding the resin
composition for molding in the present embodiment through compression molding under
the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, a curing
time of 600 seconds, at 10 GHz is, for example, 10 to 20. The relative dielectric
constant of the cured product at 10 GHz is preferably 11 to 18 and more preferably
12 to 17 from the viewpoint of miniaturization of electronic components such as an
antenna.
[0120] The above-described relative dielectric constant is measured using a dielectric constant
measurement device (for example, Agilent Technologies, product name "Network Analyzer
N5227A") at a temperature of 25±3°C.
[0121] The dielectric loss tangent of a cured product, obtained by molding the resin composition
for molding in the present embodiment through compression molding under the conditions
of a mold temperature of 175°C, a molding pressure of 6.9 MPa, a curing time of 600
seconds, at 10 GHz is, for example, 0.020 or less. The dielectric loss tangent of
the cured product at 10 GHz is preferably 0.018 or less and more preferably 0.015
or less from the viewpoint of reducing transmission loss. The lower limit value of
the dielectric loss tangent of the cured product at 10 GHz is not particularly limited,
and is, for example, 0.005.
[0122] The above-described dielectric loss tangent is measured using a dielectric constant
measurement device (for example, Agilent Technologies, product name "Network Analyzer
N5227A") at a temperature of 25±3°C.
[0123] The flow distance (hereinafter, also referred to as "spiral flow") when a resin composition
for molding is molded using a mold for measuring a spiral flow according to EMMI-1-66
under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa,
and a curing time of 90 seconds is preferably 80 cm or more, more preferably 100 cm
or more, and still more preferably 120 cm or more. The upper limit value of the spiral
flow is not particularly limited, and is, for example, 200 cm.
[0124] The gel time of the resin composition for molding at 175°C is preferably 30 seconds
to 90 seconds and more preferably 40 seconds to 60 seconds.
[0125] The gel time at 175°C is measured as follows. Specifically, the measurement of the
gel time using Curelastometer of JSR Trading Co., Ltd. is performed on 3 g of a sample
of the resin composition for molding at a temperature of 175°C, and the time until
a torque curve rises is measured as gel time (sec).
(Application of Resin Composition for Molding)
[0126] The resin composition for molding in the present embodiment can be applied to, for
example, production of an electronic component apparatus to be described below, particularly
to production of a high frequency device.
[0127] The resin composition for molding in the present embodiment is particularly suitable
for an antenna-in-package (AiP) in a high frequency device in which an antenna placed
on a support member is sealed with the resin composition for molding.
<Electronic Component Apparatus>
[0128] An electronic component apparatus which is an embodiment of the present disclosure
includes: a support member; an electronic component placed on the support member;
and a cured product of the resin composition for molding which seals the electronic
component.
[0129] Examples of electronic component apparatuses include ones (for example, a high frequency
device) obtained by sealing an electronic component region obtained by mounting electronic
components (such as active elements including semiconductor chips, transistors, diodes,
thyristors, passive elements including capacitors, resistors, and coils, and antennas)
on support members such as lead frames, wired tape carriers, wiring boards, glass,
silicon wafers, organic substrates with a resin composition for molding.
[0130] The types of the above-described support members are not particularly limited, and
generally used support members can be used for manufacturing an electronic component
apparatus.
[0131] The above-described electronic components may contain an antenna or may contain an
antenna and elements in addition to the antenna. The above-described antenna is not
limited as long as it plays a role of an antenna, and may be an antenna element or
may be wiring.
[0132] In addition, in the electronic component apparatus of the present embodiment, other
electronic components may be arranged on the surface of the support member opposite
to the surface on which the above-described electronic components are arranged as
necessary. The other electronic components may be sealed with the resin composition
for molding or with other resin compositions, or may not be sealed.
(Method for Manufacturing Electronic Component Apparatus)
[0133] A method for manufacturing an electronic component apparatus according to the present
embodiment includes a step of arranging electronic components on a support member
and a step of sealing the electronic components with the resin composition for molding.
[0134] The method for carrying out the above-described each step is not particularly limited,
and can be carried out through a general method. In addition, the types of support
members and electronic components used for manufacturing an electronic component apparatus
are not particularly limited, and support members and electronic components generally
used for manufacturing an electronic component apparatus can be used.
[0135] Examples of methods for sealing electronic components using the resin composition
for molding include a low-pressure transfer molding method, an injection molding method,
and a compression molding method. Among these, a low-pressure transfer molding method
is common.
[Examples]
[0136] Hereinafter, the above-described embodiment will be described in detail using examples,
but the scope of the above-described embodiment is not limited to these examples.
<Preparation of Resin Composition for Molding>
[0137] The components shown below are mixed at the formulation ratios (parts by mass) shown
in Tables 1 to 3 to prepare resin compositions for molding of examples and a comparative
example. These resin compositions for molding are solids at normal temperature and
pressure.
[0138] In the tables, blanks mean that the component is not contained.
[0139] In addition, the content ("total content (% by volume)" in the tables) of an inorganic
filler with respect to an entire resin composition for molding, the total content
("specific content (% by volume)" in the tables) of specific fillers with respect
to an entire resin composition for molding, the total content ("specific proportion
(% by volume)" in the tables) of specific fillers with respect to the entire inorganic
filler used, and the relative dielectric constant ("dielectric constant of entire
filler" in the tables) of the entire inorganic filler at 10 GHz are also shown in
the tables.
[0140]
- Epoxy resin 1: Triphenylmethane-type epoxy resin, epoxy equivalent of 167 g/eq (Mitsubishi
Chemical Corporation, product name "1032H60")
- Epoxy resin 2: Biphenyl-type epoxy resin, epoxy equivalent of 192 g/eq (Mitsubishi
Chemical Corporation, product name "YX-4000")
- Epoxy resin 3: O-cresol novolac-type epoxy resin, epoxy equivalent of 200 g/eq ("N500P"
manufactured by DIC CORPORATION)
- Epoxy resin 4: Biphenyl aralkyl-type epoxy resin, epoxy equivalent of 274 g/eq (Nippon
Kayaku Co., Ltd., product name "NC-3000")
- Curing agent 1: Active ester compound, DIC CORPORATION, product name "EXB-8"
- Curing agent 2: Phenol curing agent, phenol aralkyl resin, hydroxyl equivalent of
205 g/eq (Meiwa Plastic Industries, Ltd., product name "MEH7851 series")
- Inorganic filler 1: Calcium titanate particles, non-calcined specific filler, volume
average particle diameter of 4 µm, polyhedron shape
- Inorganic filler 2: Calcium titanate particles, non-calcined specific filler, volume
average particle diameter of 0.2 µm, polyhedron shape
- Inorganic filler 3: Strontium titanate particles, non-calcined specific filler, volume
average particle diameter of 5 µm, polyhedron shape
- Inorganic filler 4: Barium titanate particles, non-calcined other fillers, volume
average particle diameter of 6.6 µm, spherical shape
- Inorganic filler 5: Alumina particles, other fillers, volume average particle diameter
of 5.7 µm, spherical shape
- Inorganic filler 6: Alumina particles, other fillers, volume average particle diameter
of 0.7 µm, spherical shape
- Inorganic filler 7: Silica particles, other fillers, volume average particle diameter
of 31 µm, spherical shape
- Inorganic filler 8: Silica particles, other fillers, volume average particle diameter
of 6.6 µm, spherical shape
- Inorganic filler 9: Silica particles, other fillers, volume average particle diameter
of 0.5 µm, spherical shape
- Curing promoter: Triphenylphosphine/1,4-benzoquinone adduct
- Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.,
product name "KBM-573")
- Releasing agent: Montanic acid ester wax (Clariant Japan K.K., product name "HW-E")
- Stress relaxation agent: Polyether-based silicone compound (Momentive Performance
Materials, product name "SIM768E")
- Coloring agent: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")
[0141] The volume average particle diameter of the above-described inorganic fillers is
a value obtained through the following measurement.
[0142] Specifically, an inorganic filler is first added to a dispersion medium (water) in
a range of 0.01 mass% to 0.1 mass%, and the mixture is dispersed in a bath-type ultrasonic
cleaner for 5 minutes.
[0143] 5 mL of the obtained dispersion was injected into a cell, and the particle size distribution
was measured at 25°C using a laser diffraction-scattering type particle size distribution
measurement device (HORIBA, Ltd., LA920).
[0144] The particle diameter at an integrated value of 50% in the obtained particle size
distribution was set to a volume average particle diameter.
<Evaluation of Resin Composition for Molding>
(Relative Dielectric Constant and Dielectric Loss Tangent)
[0145] Each resin composition for molding was added to a vacuum hand press machine, molded
under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa,
and a curing time of 600 seconds, and post-cured at 175°C for 6 hours to obtain a
plate-like cured product (a length of 12.5 mm, a width of 25 mm, and a thickness of
0.2 mm). This plate-like cured product was used as a test piece to measure a relative
dielectric constant and a dielectric loss tangent at a temperature of 25±3°C and 10
GHz using a dielectric constant measurement device (Agilent Technologies, product
name "Network Analyzer N5227A"). The results are shown in the tables (the "relative
dielectric constant" and the "dielectric loss tangent" in the tables).
(Fluidity: Spiral Flow)
[0146] Each resin composition for molding was molded using a mold for measuring a spiral
flow according to EMMI-1-66 under the conditions of a mold temperature of 180°C, a
molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a flow distance
(cm). The results are shown in the tables ("flow distance (cm)" in the tables).
(Gel Time)
[0147] The measurement of the gel time using Curelastometer of JSR Trading Co., Ltd. was
performed on 3 g of each resin composition for molding at a temperature of 175°C,
and the time until a torque curve rose was regarded as gel time. The results are shown
in the tables ("gel time (seconds)" in the tables).
(Moldability)
[0148] The moldability was evaluated as follows.
[0149] Specifically, each resin composition for molding was molded using Apic Yamada Press
(G-Line Press) under the conditions of 180°C, 6.9 MPa, and 90 s to produce a molded
product having a thickness of 0.5 mm. A flow mark was visually observed on the obtained
molded product. The evaluation criteria are as follows. The results are shown in the
tables.
- A: There is no flow mark that can be visually observed.
- B: Flow marks where slight shading can be observed in an area less than one-third
of a molded product from an air vent are generated.
- C: Flow marks are generated in an area less than one-third of a molded product from
an air vent.
- D: Flow marks are generated in an area greater than or equal to one-third of a molded
product from an air vent.
[Table 1]
Item |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
Example 6 |
Example 7 |
Composition |
Epoxy resin 1 |
70.1 |
70.1 |
70.1 |
70.1 |
|
|
70.1 |
Epoxy resin 2 |
29.9 |
29.9 |
29.9 |
29.9 |
29.9 |
29.9 |
29.9 |
Epoxy resin 3 |
|
|
|
|
70.1 |
|
|
Epoxy resin 4 |
|
|
|
|
|
70.1 |
|
Curing agent 1 |
119.0 |
119.0 |
119.0 |
119.0 |
106.0 |
86.0 |
119.0 |
Curing agent 2 |
|
|
|
|
|
|
|
Curing promoter |
4.3 |
4.0 |
4.3 |
4.3 |
4.0 |
4.0 |
4.0 |
Coupling agent |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
Releasing agent |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
Stress relaxation agent |
10.0 |
10.0 |
10.0 |
5.0 |
10.0 |
10.0 |
10.0 |
Coloring agent |
|
|
|
|
|
|
|
Inorganic filler 1 |
510.0 |
551.0 |
793.0 |
599.0 |
523.0 |
478.0 |
630.0 |
Inorganic filler 2 |
128.0 |
158.0 |
199.0 |
251.0 |
150.0 |
137.0 |
158.0 |
Inorganic filler 3 |
|
|
|
|
|
|
|
Inorganic filler 4 |
|
|
|
|
|
|
|
Inorganic filler 5 |
608.0 |
827.0 |
946.0 |
1574.0 |
784.0 |
718.0 |
|
Inorganic filler 6 |
|
|
|
|
|
|
|
Inorganic filler 7 |
|
|
|
|
|
|
|
Inorganic filler 8 |
|
|
|
|
|
|
435.0 |
Inorganic filler 9 |
|
|
|
|
|
|
|
Total |
1488.3 |
1778 |
2180.3 |
2661.3 |
1686 |
1542 |
1465 |
Filler |
Total content (% by volume) |
60 |
65 |
70 |
75 |
65 |
65 |
65 |
Specific content (% by volume) |
30 |
29.25 |
35 |
25.5 |
29.25 |
29.25 |
32.5 |
Specific proportion (% by volume) |
50 |
45 |
50 |
34 |
45 |
45 |
50 |
Dielectric constant of entire filler |
20.5 |
18.8 |
20.5 |
15.2 |
18.8 |
18.8 |
18.3 |
Evaluation |
Relative dielectric constant |
15.4 |
15.3 |
17.6 |
14.7 |
15.0 |
14.8 |
15.1 |
Dielectric loss tangent |
0.007 |
0.006 |
0.007 |
0.006 |
0.006 |
0.006 |
0.006 |
Flow distance (cm) |
150 |
130 |
120 |
100 |
160 |
165 |
>200 |
Gel time (seconds) |
53 |
58 |
62 |
70 |
55 |
60 |
75 |
Moldability |
A |
A |
B |
B |
A |
A |
B |
[Table 2]
Item |
Example 8 |
Example 9 |
Example 10 |
Example 11 |
Example 12 |
Example 13 |
Example 14 |
Composition |
Epoxy resin 1 |
70.1 |
70.1 |
70.1 |
|
70.1 |
70.1 |
70.1 |
Epoxy resin 2 |
29.9 |
29.9 |
29.9 |
25.0 |
29.9 |
29.9 |
29.9 |
Epoxy resin 3 |
|
|
|
|
|
|
|
Epoxy resin 4 |
|
|
|
75.0 |
|
|
|
Curing agent 1 |
119.0 |
119.0 |
119.0 |
|
119.0 |
119.0 |
119.0 |
Curing agent 2 |
|
|
|
80.3 |
|
|
|
Curing promoter |
4.0 |
4.0 |
3.0 |
3.5 |
4.0 |
4.0 |
4.3 |
Coupling agent |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
8.0 |
Releasing agent |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
1.0 |
Stress relaxation agent |
10.0 |
10.0 |
10.0 |
10.0 |
|
10.0 |
10.0 |
Coloring agent |
|
|
|
|
|
|
6.6 |
Inorganic filler 1 |
551.0 |
551.0 |
630.0 |
465.0 |
530.0 |
|
648.0 |
Inorganic filler 2 |
158.0 |
158.0 |
158.0 |
200.0 |
152.0 |
|
163.0 |
Inorganic filler 3 |
|
|
|
|
|
902.0 |
|
Inorganic filler 4 |
|
|
|
|
|
|
|
Inorganic filler 5 |
752.0 |
752.0 |
|
635.0 |
794.0 |
547.0 |
648.0 |
Inorganic filler 6 |
|
75.0 |
|
|
|
|
|
Inorganic filler 7 |
|
|
435.0 |
|
|
|
|
Inorganic filler 8 |
|
|
|
|
|
|
|
Inorganic filler 9 |
44.0 |
|
|
|
|
|
|
Total |
1747 |
1778 |
1464 |
1531.5 |
1708 |
1691 |
1707.9 |
Filler |
Total content (% by volume) |
65 |
65 |
65 |
65 |
65 |
60 |
65 |
Specific content (% by volume) |
29.25 |
32.5 |
32.5 |
32.5 |
29.25 |
33 |
29.25 |
Specific proportion (% by volume) |
45 |
50 |
50 |
50 |
45 |
55 |
45 |
Dielectric constant of entire filler |
18.6 |
18.8 |
18.3 |
18.6 |
18.8 |
23.3 |
18.8 |
Evaluation |
Relative dielectric constant |
15.2 |
15.4 |
15.0 |
15.0 |
15.3 |
15.9 |
16.0 |
Dielectric loss tangent |
0.006 |
0.007 |
0.006 |
0.020 |
0.006 |
0.007 |
0.009 |
Flow distance (cm) |
130 |
130 |
>200 |
180 |
140 |
140 |
130 |
Gel time (seconds) |
55 |
60 |
75 |
50 |
55 |
53 |
59 |
Moldability |
A |
A |
B |
B |
B |
B |
A |
[Table 3]
Item |
Example 15 |
Example 16 |
Example 17 |
Comparative Example 1 |
Composition |
Epoxy resin 1 |
70.1 |
70.1 |
70.1 |
70.1 |
Epoxy resin 2 |
29.9 |
29.9 |
29.9 |
29.9 |
Epoxy resin 3 |
|
|
|
|
Epoxy resin 4 |
|
|
|
|
Curing agent 1 |
119.0 |
119.0 |
119.0 |
119.0 |
Curing agent 2 |
|
|
|
|
Curing promoter |
4.3 |
4.3 |
4.0 |
4.0 |
Coupling agent |
8.0 |
8.0 |
8.0 |
8.0 |
Releasing agent |
1.0 |
1.0 |
1.0 |
1.0 |
Stress relaxation agent |
10.0 |
10.0 |
10.0 |
10.0 |
Coloring agent |
|
|
|
|
Inorganic filler 1 |
255.0 |
1019.0 |
|
|
Inorganic filler 2 |
128.0 |
256.0 |
|
|
Inorganic filler 3 |
|
|
1021.0 |
|
Inorganic filler 4 |
|
|
|
1492.0 |
Inorganic filler 5 |
852.0 |
1216.0 |
1134.0 |
|
Inorganic filler 6 |
|
|
|
900.0 |
Inorganic filler 7 |
|
|
|
|
Inorganic filler 8 |
|
|
|
|
Inorganic filler 9 |
|
|
|
|
Total |
1477.3 |
2733.3 |
2397 |
2634 |
Filler |
Total content (% by volume) |
60 |
75 |
70 |
70 |
Specific content (% by volume) |
18 |
37.5 |
39 |
0 |
Specific proportion (% by volume) |
30 |
50 |
56 |
0 |
Dielectric constant of entire filler |
13.9 |
20.6 |
21.9 |
26.9 |
Evaluation |
Relative dielectric constant |
11.6 |
18.6 |
19.8 |
14.0 |
Dielectric loss tangent |
0.006 |
0.007 |
0.0072 |
0.040 |
Flow distance (cm) |
140 |
100 |
80 |
180 |
Gel time (seconds) |
53 |
65 |
60 |
60 |
Moldability |
A |
C |
C |
D |
[0150] As shown in the tables, the resin compositions for molding of the examples have a
long flow distance and favorable moldability compared to the resin composition for
molding of the comparative example, and both a high relative dielectric constant and
a low dielectric loss tangent in a cured product after molding are achieved.
[0152] All of the references, the patent application, and the technical standard described
in the present specification are incorporated in the present specification by reference
to the same extent as in a case where incorporation of individual documents, patent
application, and technical standard by reference is specifically and individually
written.